Dual Catalyst Composition

ABSTRACT

The present invention also relates to a polymerization process using said composition. The invention further relates to olefin polymers at least partially catalyzed by said catalyst composition and articles comprising said olefin polymers.

FIELD OF INVENTION

The invention relates to the new dual catalyst, in particular dual sitecatalysts for polymerization reactions.

BACKGROUND OF THE INVENTION

In the field of polymer, constant mechanical properties improvement ismandatory. It was achieved in the last few years using metallocenecatalyst combined with cascade reactor to make tailor made bimodalresins. However, the requirement of multiple reactors leads to increasedcosts for both construction and operation, and this can be overcomeusing dual-site catalysts in a single reactor.

In the prior art, the first obvious strategy was multiple separatecatalyst injection. Although, this process showed high flexibility,several drawbacks can be highlighted: multiple catalysts injections leadto increased costs and polymer homogeneity was difficult to achieve.

The strategy of using a dual-site catalyst in a single reactor seemedtherefore to be a good alternative. However, this technology suffersfrom the difficulty to control properly the heterogenization and moreimportantly the activation. This might be related to the differentbehavior of metallocene during the heterogenization process typicallyleading to a dominating structure while others seem inactive. Moreover,in several examples in the literature, some combinations suffer of alack of reactivity or works only in specific conditions or in a specificprocess. The challenge is to find the right combination of metallocenesto avoid these drawbacks.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a new dualcatalyst avoiding the above mentioned drawbacks.

In a first aspect, the present invention provides a catalyst compositioncomprising:

catalyst component A comprising a bridged metallocene compound with twogroups independently selected from indenyl or tetrahydroindenyl, eachgroup being unsubstituted or substituted;catalyst component B comprising a bridged metallocene compound with asubstituted or unsubstituted cyclopentadienyl group and a substituted orunsubstituted fluorenyl group;an optional activator; an optional support; and an optional co-catalyst.

In a preferred first aspect, the present invention provides a catalystcomposition comprising: catalyst component A comprising a bridgedmetallocene compound with two indenyl groups each indenyl beingindependently substituted with one or more substituents, wherein atleast one of the substituent is an aryl or heteroaryl; preferablywherein the aryl or heteroaryl substituent is on the 3-position on eachindenyl;

catalyst component B comprising a bridged metallocene compound with asubstituted or unsubstituted cyclopentadienyl group and a substituted orunsubstituted fluorenyl group;an optional activator; an optional support; and an optional co-catalyst.

In a second aspect, the present invention provides an olefinpolymerization process, the process comprising: contacting at least onecatalyst composition according to the first aspect, or preferred firstaspect, with an olefin monomer, optionally hydrogen, and optionally oneor more olefin co-monomers; and polymerizing the monomer, and theoptionally one or more olefin co-monomers, in the presence of the atleast one catalyst composition, and optional hydrogen, thereby obtaininga polyolefin.

In a third aspect, the present invention provides, an olefin polymer atleast partially catalyzed by at least one catalyst composition accordingto the first aspect, or preferred first aspect, or produced by theprocess according to the second aspect of the invention.

The present invention also encompasses an article comprising the olefinpolymer according to the third aspect.

The invention provides a composition comprising a dual catalyst whichmeans a catalyst particle with two metallocene active sites on a singlecarrier. For example, catalyst “A” can produce short chains withoutco-monomer while catalyst “B” can produce longer chains with highconcentration of co-monomer. The catalyst composition can be used insingle reactor processes (slurry loop and/or gas phase) or even inmultimodal processes.

The invention overcomes the drawbacks of the aforementioned strategies.Such catalyst compositions can be used to produce, for example,ethylene-copolymers having broad molecular weight distributions, idealco-monomer incorporation to improve mechanical properties and a higheractivity compare to other systems. After the polymer is produced, it maybe formed into various articles, including but not limited to, filmproducts, caps and closures, rotomoulding, grass yarn, etc.

The independent and dependent claims set out particular and preferredfeatures of the invention. Features from the dependent claims may becombined with features of the independent or other dependent claims asappropriate.

The present invention will now be further described. In the followingpassages, different aspects of the invention are defined in more detail.Each aspect so defined may be combined with any other aspect or aspectsunless clearly indicated to the contrary. In particular, any feature orstatement indicated as being preferred or advantageous may be combinedwith any other features or statements indicated as being preferred oradvantageous.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 represents a graph plotting the activity of different catalystcompositions Met1/Met5 as a function of hydrogen concentration.

FIG. 2 represents a graph plotting the molecular weight distribution(logarithm of molecular weight) and the ratio CH₃/CH₂ of a polymerobtained using a catalyst composition Met1/Met5.

FIG. 3 represents a graph plotting the activity of a catalystcomposition Met4/Met5 as a function of hydrogen concentration.

FIG. 4 represents a graph plotting the melt index as a function ofhydrogen concentration for polymers produced using catalyst compositionMet4/Met5.

FIG. 5 represents a graph plotting the molecular weight distribution(logarithm of molecular weight) and the ratio CH₃/CH₂ of a polymerobtained using catalyst composition Met4/Met5 via example 6polymerization.

FIG. 6 represents a graph plotting the molecular weight distribution(logarithm of molecular weight) and the ratio CH₃/CH₂ of a polymerobtained using catalyst composition Met6/Met5 via comparative example 7polymerization.

FIG. 7 represents a graph plotting the molecular weight distribution(logarithm of molecular weight) and the ratio CH₃/CH₂ of a polymerobtained using catalyst composition Met4/Met5 via example 8polymerization.

DETAILED DESCRIPTION OF THE INVENTION

Before the present compounds, processes, articles, and uses encompassedby the invention are described, it is to be understood that thisinvention is not limited to particular compounds, processes, articles,and uses described, as such compounds, processes, articles, and usesmay, of course, vary. It is also to be understood that the terminologyused herein is not intended to be limiting, since the scope of thepresent invention will be limited only by the appended claims.

Unless otherwise defined, all terms used in disclosing the invention,including technical and scientific terms, have the meaning as commonlyunderstood by one of ordinary skill in the art to which this inventionbelongs. By means of further guidance, definitions for the terms used inthe description are included to better appreciate the teaching of thepresent invention. When describing the compounds, processes, articles,and uses of the invention, the terms used are to be construed inaccordance with the following definitions, unless the context dictatesotherwise.

As used herein, the singular forms “a”, “an”, and “the” include bothsingular and plural referents unless the context clearly dictatesotherwise. By way of example, “a resin” means one resin or more than oneresin.

The terms “comprising”, “comprises” and “comprised of” as used hereinare synonymous with “including”, “includes” or “containing”, “contains”,and are inclusive or open-ended and do not exclude additional,non-recited members, elements or method steps. The terms “comprising”,“comprises” and “comprised of” also include the term “consisting of”.

The recitation of numerical ranges by endpoints includes all integernumbers and, where appropriate, fractions subsumed within that range(e.g. 1 to 5 can include 1, 2, 3, 4 when referring to, for example, anumber of elements, and can also include 1.5, 2, 2.75 and 3.80, whenreferring to, for example, measurements). The recitation of end pointsalso includes the end point values themselves (e.g. from 1.0 to 5.0includes both 1.0 and 5.0). Any numerical range recited herein isintended to include all sub-ranges subsumed therein.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment of the present invention. Thus, appearances of the phrases“in one embodiment” or “in an embodiment” in various places throughoutthis specification are not necessarily all referring to the sameembodiment, but may. Furthermore, the particular features, structures orcharacteristics may be combined in any suitable manner, as would beapparent to a person skilled in the art from this disclosure, in one ormore embodiments. Furthermore, while some embodiments described hereininclude some but not other features included in other embodiments,combinations of features of different embodiments are meant to be withinthe scope of the invention, and form different embodiments, as would beunderstood by those in the art. For example, in the following claims andstatements, any of the embodiments can be used in any combination.

Whenever the term “substituted” is used herein, it is meant to indicatethat one or more hydrogen atoms on the atom indicated in the expressionusing “substituted” is replaced with a selection from the indicatedgroup, provided that the indicated atom's normal valence is notexceeded, and that the substitution results in a chemically stablecompound, i.e. a compound that is sufficiently robust to surviveisolation from a reaction mixture. Preferred substituents for theindenyl, tetrahydroindenyl, cyclopentadienyl and fluorenyl groups, canbe selected from the group comprising alkyl, alkenyl, cycloalkyl, aryl,alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)₃, heteroalkyl; whereineach R¹⁰ is independently hydrogen, alkyl, or alkenyl. Preferably, eachindenyl is substituted with at least one aryl or heteroaryl, morepreferably aryl; preferably wherein the aryl or heteroaryl substituentis on the 3-position on each indenyl; the indenyl can be furthersubstituted with one or more substituents selected from the groupcomprising alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl,arylalkyl, halogen, Si(R¹⁰)₃, heteroalkyl; wherein each R¹⁰ isindependently hydrogen, alkyl, or alkenyl.

The term “halo” or “halogen” as a group or part of a group is genericfor fluoro, chloro, bromo, iodo.

The term “alkyl” as a group or part of a group, refers to a hydrocarbylgroup of formula C_(n)H_(2n+1) wherein n is a number greater than orequal to 1. Alkyl groups may be linear or branched and may besubstituted as indicated herein. Generally, alkyl groups of thisinvention comprise from 1 to 20 carbon atoms, preferably from 1 to 10carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from1 to 4 carbon atoms. When a subscript is used herein following a carbonatom, the subscript refers to the number of carbon atoms that the namedgroup may contain. For example, the term “C₁₋₂₀alkyl”, as a group orpart of a group, refers to a hydrocarbyl group of formula —C_(n)H_(2n+1)wherein n is a number ranging from 1 to 20. Thus, for example,“C₁₋₈alkyl” includes all linear or branched alkyl groups with between 1and 8 carbon atoms, and thus includes methyl, ethyl, n-propyl, i-propyl,butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl); pentyl andits isomers, hexyl and its isomers, etc. A “substituted alkyl” refers toan alkyl group substituted with one or more substituent(s) (for example1 to 3 substituent(s), for example 1, 2, or 3 substituent(s)) at anyavailable point of attachment.

When the suffix “ene” is used in conjunction with an alkyl group, i.e.“alkylene”, this is intended to mean the alkyl group as defined hereinhaving two single bonds as points of attachment to other groups. As usedherein, the term “alkylene” also referred as “alkanediyl”, by itself oras part of another substituent, refers to alkyl groups that aredivalent, i.e., with two single bonds for attachment to two othergroups. Alkylene groups may be linear or branched and may be substitutedas indicated herein. Non-limiting examples of alkylene groups includemethylene (—CH₂—), ethylene (—CH₂—CH₂—), methylmethylene (—CH(CH₃)—),1-methyl-ethylene (—CH(CH₃)—CH₂—), n-propylene (—CH₂—CH₂—CH₂—),2-methylpropylene (—CH₂—CH(CH₃)—CH₂—), 3-methylpropylene(—CH₂—CH₂—CH(CH₃)—), n-butylene (—CH₂—CH₂—CH₂—CH₂—), 2-methylbutylene(—CH₂—CH(CH₃)—CH₂—CH₂—), 4-methylbutylene (—CH₂—CH₂—CH₂—CH(CH₃)—),pentylene and its chain isomers, hexylene and its chain isomers.

The term “alkenyl” as a group or part of a group, refers to anunsaturated hydrocarbyl group, which may be linear, or branched,comprising one or more carbon-carbon double bonds. Generally, alkenylgroups of this invention comprise from 3 to 20 carbon atoms, preferablyfrom 3 to 10 carbon atoms, preferably from 3 to 8 carbon atoms. When asubscript is used herein following a carbon atom, the subscript refersto the number of carbon atoms that the named group may contain. Examplesof C₃₋₂₀alkenyl groups are ethenyl, 2-propenyl, 2-butenyl, 3-butenyl,2-pentenyl and its isomers, 2-hexenyl and its isomers, 2,4-pentadienyl,and the like.

The term “alkoxy” or “alkyloxy”, as a group or part of a group, refersto a group having the formula —OR^(b) wherein R^(b) is alkyl as definedherein above. Non-limiting examples of suitable alkoxy include methoxy,ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy,pentyloxy and hexyloxy.

The term “cycloalkyl”, as a group or part of a group, refers to a cyclicalkyl group, that is a monovalent, saturated, hydrocarbyl group having 1or more cyclic structure, and comprising from 3 to 20 carbon atoms, morepreferably from 3 to 10 carbon atoms, more preferably from 3 to 8 carbonatoms; more preferably from 3 to 6 carbon atoms. Cycloalkyl includes allsaturated hydrocarbon groups containing 1 or more rings, includingmonocyclic, bicyclic groups or tricyclic. The further rings ofmulti-ring cycloalkyls may be either fused, bridged and/or joinedthrough one or more spiro atoms. When a subscript is used hereinfollowing a carbon atom, the subscript refers to the number of carbonatoms that the named group may contain. For example, the term“C₃₋₂₀cycloalkyl”, a cyclic alkyl group comprising from 3 to 20 carbonatoms. For example, the term “C₃₋₁₀cycloalkyl”, a cyclic alkyl groupcomprising from 3 to 10 carbon atoms. For example, the term“C₃₋₈cycloalkyl”, a cyclic alkyl group comprising from 3 to 8 carbonatoms. For example, the term “C₃₋₆cycloalkyl”, a cyclic alkyl groupcomprising from 3 to 6 carbon atoms. Examples of C₃₋₁₂cycloalkyl groupsinclude but are not limited to adamantly, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,bicycle[2.2.1]heptan-2yl, (1S,4R)-norbornan-2-yl,(1R,4R)-norbornan-2-yl, (1S,4S)-norbornan-2-yl, (1R,4S)-norbornan-2-yl.

When the suffix “ene” is used in conjunction with a cycloalkyl group,i.e. cycloalkylene, this is intended to mean the cycloalkyl group asdefined herein having two single bonds as points of attachment to othergroups. Non-limiting examples of “cycloalkylene” include1,2-cyclopropylene, 1,1-cyclopropylene, 1,1-cyclobutylene,1,2-cyclobutylene, 1,3-cyclopentylene, 1,1-cyclopentylene, and1,4-cyclohexylene.

Where an alkylene or cycloalkylene group is present, connectivity to themolecular structure of which it forms part may be through a commoncarbon atom or different carbon atom. To illustrate this applying theasterisk nomenclature of this invention, a C₃alkylene group may be forexample *—CH₂CH₂CH₂—*, *—CH(—CH₂CH₃)—* or *—CH₂CH(—CH₃)—*. Likewise aC₃cycloalkylene group may be

The term “cycloalkenyl” as a group or part of a group, refers to anon-aromatic cyclic alkenyl group, with at least one site (usually 1 to3, preferably 1) of unsaturation, namely a carbon-carbon, sp2 doublebond; preferably having from 5 to 20 carbon atoms more preferably from 5to 10 carbon atoms, more preferably from 5 to 8 carbon atoms, morepreferably from 5 to 6 carbon atoms. Cycloalkenyl includes allunsaturated hydrocarbon groups containing 1 or more rings, includingmonocyclic, bicyclic or tricyclic groups. The further rings may beeither fused, bridged and/or joined through one or more spiro atoms.When a subscript is used herein following a carbon atom, the subscriptrefers to the number of carbon atoms that the named group may contain.For example, the term “C₅₋₂₀cycloalkenyl”, a cyclic alkenyl groupcomprising from 5 to 20 carbon atoms. For example, the term“C₅₋₁₀cycloalkenyl”, a cyclic alkenyl group comprising from 5 to 10carbon atoms. For example, the term “C₅₋₈cycloalkenyl”, a cyclic alkenylgroup comprising from 5 to 8 carbon atoms. For example, the term“C₅₋₆cycloalkyl”, a cyclic alkenyl group comprising from 5 to 6 carbonatoms. Examples include, but are not limited to: cyclopentenyl (—C₅H₇),cyclopentenylpropylene, methylcyclohexenylene and cyclohexenyl (—C₆H₉).The double bond may be in the cis or trans configuration.

The term “cycloalkenylalkyl”, as a group or part of a group, means analkyl as defined herein, wherein at least one hydrogen atom is replacedby at least one cycloalkenyl as defined herein.

The term “cycloalkoxy”, as a group or part of a group, refers to a grouphaving the formula —OR^(h) wherein R^(h) is cycloalkyl as defined hereinabove.

The term “aryl”, as a group or part of a group, refers to apolyunsaturated, aromatic hydrocarbyl group having a single ring (i.e.phenyl) or multiple aromatic rings fused together (e.g. naphthyl), orlinked covalently, typically containing 6 to 20 atoms; preferably 6 to10, wherein at least one ring is aromatic. The aromatic ring mayoptionally include one to two additional rings (either cycloalkyl,heterocyclyl or heteroaryl) fused thereto. Examples of suitable arylinclude C₆₋₂₀aryl, preferably C₆₋₁₀aryl, more preferably C₆₋₈aryl.Non-limiting examples of aryl comprise phenyl, biphenylyl, biphenylenyl,or 1- or 2-naphthanelyl; 1-, 2-, 3-, 4-, 5- or 6-tetralinyl (also knownas “1,2,3,4-tetrahydronaphtalene); 1-, 2-, 3-, 4-, 5-, 6-, 7- or8-azulenyl, 4-, 5-, 6 or 7-indenyl; 4- or 5-indanyl; 5-, 6-, 7- or8-tetrahydronaphthyl; 1,2,3,4-tetrahydronaphthyl; and1,4-dihydronaphthyl; 1-, 2-, 3-, 4- or 5-pyrenyl. A “substituted aryl”refers to an aryl group having one or more substituent(s) (for example1, 2 or 3 substituent(s), or 1 to 2 substituent(s)), at any availablepoint of attachment.

The term “aryloxy”, as a group or part of a group, refers to a grouphaving the formula —OR^(g) wherein R^(g) is aryl as defined hereinabove.

The term “arylalkyl”, as a group or part of a group, means an alkyl asdefined herein, wherein at least one hydrogen atom is replaced by atleast one aryl as defined herein. Non-limiting examples of arylalkylgroup include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl,3-(2-naphthyl)-butyl, and the like.

The term “alkylaryl” as a group or part of a group, means an aryl asdefined herein wherein at least one hydrogen atom is replaced by atleast one alkyl as defined herein. Non-limiting example of alkylarylgroup include p-CH₃—R^(g)—, wherein R^(g) is aryl as defined hereinabove.

The term “arylalkyloxy” or “aralkoxy” as a group or part of a group,refers to a group having the formula —O—R^(a)—R^(g) wherein R^(g) isaryl, and R^(a) is alkylene as defined herein above.

The term “heteroalkyl” as a group or part of a group, refers to anacyclic alkyl wherein one or more carbon atoms are replaced by at leastone heteroatom selected from the group comprising O, Si, S, B, and P,with the proviso that said chain may not contain two adjacentheteroatoms. This means that one or more —CH₃ of said acyclic alkyl canbe replaced by —OH for example and/or that one or more —CR₂— of saidacyclic alkyl can be replaced by O, Si, S, B, and P.

The term “aminoalkyl” as a group or part of a group, refers to the group—R^(j)—NR^(k)R^(l) wherein R^(j) is alkylene, R^(k) is hydrogen or alkylas defined herein, and R^(l) is hydrogen or alkyl as defined herein.

The term “heterocyclyl” as a group or part of a group, refers tonon-aromatic, fully saturated or partially unsaturated cyclic groups(for example, 3 to 7 member monocyclic, 7 to 11 member bicyclic, orcontaining a total of 3 to 10 ring atoms) which have at least oneheteroatom in at least one carbon atom-containing ring. Each ring of theheterocyclic group containing a heteroatom may have 1, 2, 3 or 4heteroatoms selected from N, S, Si, Ge, where the nitrogen and sulfurheteroatoms may optionally be oxidized and the nitrogen heteroatoms mayoptionally be quaternized. The heterocyclic group may be attached at anyheteroatom or carbon atom of the ring or ring system, where valenceallows. The rings of multi-ring heterocycles may be fused, bridgedand/or joined through one or more spiro atoms.

Non limiting exemplary heterocyclic groups include aziridinyl, oxiranyl,thiiranyl, piperidinyl, azetidinyl, 2-imidazolinyl, pyrazolidinylimidazolidinyl, isoxazolinyl, oxazolidinyl, isoxazolidinyl,thiazolidinyl, isothiazolidinyl, piperidinyl, succinimidyl, 3H-indolyl,indolinyl, isoindolinyl, 2H-pyrrolyl, 1-pyrrolinyl, 2-pyrrolinyl,3-pyrrolinyl, pyrrolidinyl, 4H-quinolizinyl, 2-oxopiperazinyl,piperazinyl, homopiperazinyl, 2-pyrazolinyl, 3-pyrazolinyl,tetrahydro-2H-pyranyl, 2H-pyranyl, 4H-pyranyl, 3,4-dihydro-2H-pyranyl,oxetanyl, thietanyl, 3-dioxolanyl, 1,4-dioxanyl, 2,5-dioximidazolidinyl,2-oxopiperidinyl, 2-oxopyrrolodinyl, indolinyl, tetrahydropyranyl,tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydroquinolinyl,tetrahydroisoquinolin-1-yl, tetrahydroisoquinolin-2-yl,tetrahydroisoquinolin-3-yl, tetrahydroisoquinolin-4-yl,thiomorpholin-4-yl, thiomorpholin-4-ylsulfoxide,thiomorpholin-4-ylsulfone, 1,3-dioxolanyl, 1,4-oxathianyl,1,4-dithianyl, 1,3,5-trioxanyl, 1H-pyrrolizinyl,tetrahydro-1,1-dioxothiophenyl, N-formylpiperazinyl, and morpholin-4-yl.

Whenever used in the present invention the term “compounds” or a similarterm is meant to include the compounds of general formula (I) and/or(II) and any subgroup thereof, including all polymorphs and crystalhabits thereof, and isomers thereof (including optical, geometric andtautomeric isomers) as hereinafter defined.

The compounds of formula (I) and/or (II) or any subgroups thereof maycomprise alkenyl group, and the geometric cis/trans (or Z/E) isomers areencompassed herein. Where structural isomers are interconvertible via alow energy barrier, tautomeric isomerism (‘tautomerism’) can occur. Thiscan take the form of proton tautomerism in compounds of formula (I)containing, for example, a keto group, or so-called valence tautomerismin compounds which contain an aromatic moiety. It follows that a singlecompound may exhibit more than one type of isomerism.

Cis/trans isomers may be separated by conventional techniques well knownto those skilled in the art, for example, chromatography and fractionalcrystallization.

Preferred statements (features) and embodiments of the compositions,processes, polymers, articles, and uses of this invention are set hereinbelow. Each statement and embodiment of the invention so defined may becombined with any other statement and/or embodiment, unless clearlyindicated to the contrary. In particular, any feature indicated as beingpreferred or advantageous may be combined with any other features orstatements indicated as being preferred or advantageous. Hereto, thepresent invention is in particular captured by any one or anycombination of one or more of the below numbered statements andembodiments, with any other aspect and/or embodiment.

-   1. A catalyst composition comprising:    -   catalyst component A comprising a bridged metallocene compound        with two groups independently selected from indenyl or        tetrahydroindenyl, each group being unsubstituted or        substituted;    -   catalyst component B comprising a bridged metallocene compound        with a substituted or unsubstituted cyclopentadienyl group and a        substituted or unsubstituted fluorenyl group;    -   an optional activator; an optional support; and an optional        co-catalyst.-   2. A catalyst composition comprising:    -   catalyst component A comprising a bridged metallocene compound        with two indenyl groups each indenyl being independently        substituted with one or more substituents, wherein at least one        of the substituent is an aryl or heteroaryl, preferably aryl;        preferably wherein the aryl or heteroaryl substituent is on the        3-position on each indenyl;    -   catalyst component B comprising a bridged metallocene compound        with a substituted or unsubstituted cyclopentadienyl group and a        substituted or unsubstituted fluorenyl group;    -   an optional activator; an optional support; and an optional        co-catalyst.-   3. A catalyst composition comprising:    -   catalyst component A comprising a bridged metallocene compound        with two indenyl groups each indenyl being independently        substituted with one or more substituents, wherein at least one        of the substituent is an aryl or heteroaryl, preferably aryl;        preferably wherein the aryl or heteroaryl substituent is on the        3-position on each indenyl;    -   catalyst component B comprising a bridged metallocene compound        with a substituted or unsubstituted cyclopentadienyl group and a        substituted or unsubstituted fluorenyl group;    -   an activator; a support; and an optional co-catalyst.-   4. The composition according to any one of statements 1-3, wherein    the bridged metallocene compound of catalyst component B comprises    at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl    substituent, preferably at least one C₃₋₂₀alkenyl,    C₅₋₂₀cycloalkenyl, or C₆₋₂₀cycloalkenylalkyl substituent, more    preferably at least one C₃₋₈alkenyl, C₅₋₈cycloalkenyl, or    C₆₋₈cycloalkenylalkyl substituent.-   5. The composition according to any one of statements 1-4, wherein    the bridged metallocene compound of catalyst component B comprises    at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl substituent    on the bridge; preferably at least one C₃₋₂₀alkenyl,    C₅₋₂₀cycloalkenyl, or C₆₋₂₀cycloalkenylalkyl substituent, more    preferably at least one C₃₋₈alkenyl, C₅₋₈cycloalkenyl, or    C₆₋₈cycloalkenylalkyl substituent.-   6. The composition according to any one of statements 1-5, wherein    catalyst component B contains a C, Si, B or Ge bridging atom.-   7. The composition according to any one of statements 1-6, wherein    the activator comprises an aluminoxane compound, an organoboron or    organoborate compound, an ionizing ionic compound, or any    combination thereof, preferably wherein the activator comprises an    alumoxane compound.-   8. The composition according to any one of statements 1-7, wherein    the activator comprises at least one alumoxane compound of    formula (V) or (VI)

R^(a)—(Al(R^(a))—O)_(x)—AlR^(a) ₂  (V) for oligomeric, linearalumoxanes; or

(—Al(R^(a))—O—)_(y)  (VI) for oligomeric, cyclic alumoxanes

-   -   wherein x is 1-40, and preferably 10-20;    -   wherein y is 3-40, and preferably 3-20; and    -   wherein each R^(a) is independently selected from a C₁₋₈alkyl,        and preferably is methyl.

-   9. The composition according to any one of statements 1-8, wherein    the activator is methyl alumoxane.

-   10. The composition according to any one of statements 1-9, wherein    the catalyst composition comprises a co-catalyst.

-   11. The composition according to any one of statements 1-10, wherein    the catalyst composition comprises an organoaluminum co-catalyst.

-   12. The composition according to any one of statements 1-11, wherein    the catalyst composition comprises an organoaluminum co-catalyst    selected from the group comprising trimethylaluminum,    triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum,    triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,    diisobutylaluminum hydride, diethylaluminum ethoxide,    diethylaluminum chloride, and any combination thereof.

-   13. The composition according to any one of statements 1-12, wherein    the support comprises a solid oxide, preferably a solid inorganic    oxide, preferably, the solid oxide comprises titanated silica,    silica, alumina, silica-alumina, silica-coated alumina, aluminum    phosphate, aluminophosphate, heteropolytungstate, titania, zirconia,    magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture    thereof; preferably silica, titanated silica, silica treated with    fluoride, silica-alumina, alumina treated with fluoride, sulfated    alumina, silica-alumina treated with fluoride, sulfated    silica-alumina, silica-coated alumina, silica treated with fluoride,    sulfated silica-coated alumina, or any combination thereof.

-   14. The composition according to any one of statements 1-13, wherein    the support has a D50 of at most 50 μm, preferably of at most 40 μm,    preferably of at most 30 μm. The D50 is defined as the particle size    for which fifty percent by weight of the particles has a size lower    than the D50. The particle size may be measured by laser diffraction    analysis on a Malvern type analyzer.

-   15. The composition according to any one of statements 1-14,    comprising an alumoxane activator; and a titanated silica or silica    solid support; and an optional co-catalyst.

-   16. The composition according to any one of statements 1-15, wherein    the weight ratio of catalyst component A to catalyst component B is    in a range of from 1:9 to about 9:1, preferably the weight ratio of    catalyst component A to catalyst component B is in a range of from    1:5 to about 5:1, preferably 1:4 to 4:1.

-   17. The composition according to any one of statements 1-16, wherein    catalyst component A comprises a bridged metallocene catalyst of    formula (I), wherein

-   -   each of R¹, and R³, are independently selected from the group        consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl,        cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen,        Si(R¹⁰)₃, heteroalkyl; wherein at least one of R¹ or R³ is aryl,        wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl;        and m, n, p, q are each independently an integer selected from        0, 1, 2, 3, or 4;    -   each of R², and R⁴, are independently selected from the group        consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl,        cycloalkenylalkyl, phenyl, alkoxy, alkylaryl, arylalkyl,        halogen, Si(R¹⁰)₃, heteroalkyl; wherein at least one of R² or R⁴        is aryl, wherein each R¹⁰ is independently hydrogen, alkyl, or        alkenyl; and m, n, p, q are each independently an integer        selected from 0, 1, 2, 3, or 4;    -   L¹ is —[CR⁸R⁹]_(n)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an        integer selected from 1, 2, or 3; each of R⁸, and R⁹ are        independently selected from the group consisting of hydrogen,        alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl,        aryl, aminoalkyl, and arylalkyl; or R⁸ and R⁹ together with the        atom to which they are attached form a cycloalkyl, cycloalkenyl        or heterocyclyl;    -   M¹ is a transition metal selected from the group consisting of        zirconium, titanium, hafnium, and vanadium; and preferably is        zirconium; and    -   Q¹ and Q² are each independently selected from the group        consisting of halogen, alkyl, —N(R¹¹)₂, alkoxy, cycloalkoxy,        aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl;        wherein R¹¹ is hydrogen or alkyl.

-   18. The composition according to any one of statements 1-17, wherein    the catalyst component A contains a SiR⁸R⁹, or —[CR⁸R⁹]_(h)—    bridging group; preferably a SiR⁸R⁹ bridging group; wherein h is an    integer selected from 1, 2, or 3; each of R⁸, and R⁹ are    independently selected from the group comprising hydrogen, alkyl,    alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl,    aminoalkyl, and arylalkyl, preferably alkyl; or R⁸ and R⁹ together    with the atom to which they are attached form a cycloalkyl,    cycloalkenyl or heterocyclyl.

-   19. The composition to any one of statements 1-18, wherein catalyst    component B comprises a bridged metallocene catalyst of formula    (II), wherein

-   -   each of R⁵, R⁶, and R⁷, are independently selected from the        group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl,        cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen,        Si(R¹⁰)₃, and heteroalkyl; wherein each R¹⁰ is independently        hydrogen, alkyl, or alkenyl; and r, s, t are each independently        an integer selected from 0, 1, 2, 3, or 4;    -   L² is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an        integer selected from 1, 2, or 3; each of R⁸, and R⁹ are        independently selected from the group consisting of hydrogen,        alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl,        aryl, aminoalkyl, and arylalkyl; or R⁸ and R⁹ together with the        atom to which they are attached form a cycloalkyl, cycloalkenyl        or heterocyclyl;

-   M² is a transition metal selected from the group consisting of    zirconium, titanium, hafnium, and vanadium; and preferably is    zirconium; and

-   Q³ and Q⁴ are each independently selected from the group consisting    of halogen, alkyl, —N(R¹¹)₂, alkoxy, cycloalkoxy, aralkoxy,    cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R¹¹    is hydrogen or alkyl.

-   20. The composition according to any one of statements 1-19, wherein    catalyst component A comprises a bridged metallocene catalyst of    formula (I), wherein

-   -   each dotted line represents an optional double bond    -   each of R¹, R³ are independently selected from the group        consisting of C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀cycloalkyl,        C₅₋₂₀cycloalkenyl, C₆₋₂₀cycloalkenylalkyl, C₆₋₂₀aryl,        C₁₋₂₀alkoxy, C₇₋₂₀alkylaryl, C₇₋₂₀arylalkyl, halogen, Si(R¹⁰)₃,        and heteroC₁₋₁₂alkyl; wherein at least one of R¹ or R³ is        C₆₋₂₀aryl, preferably phenyl; wherein each R¹⁰ is independently        hydrogen, C₁₋₂₀alkyl, or C₃₋₂₀alkenyl; and m, n, p, q are each        independently an integer selected from 0, 1, 2, 3, or 4;    -   each of R², R⁴ are independently selected from the group        consisting of C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀cycloalkyl,        C₅₋₂₀cycloalkenyl, C₆₋₂₀cycloalkenylalkyl, C₆₋₂₀aryl,        C₁₋₂₀alkoxy, C₇₋₂₀alkylaryl, C₇₋₂₀arylalkyl, halogen, Si(R¹)₃,        and heteroC₁₋₁₂alkyl; wherein at least one of R² or R⁴ is        C₆₋₂₀aryl, preferably phenyl; wherein each R¹⁰ is independently        hydrogen, C₁₋₂₀alkyl, or C₃₋₂₀alkenyl; and m, n, p, q are each        independently an integer selected from 0, 1, 2, 3, or 4;    -   L¹ is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an        integer selected from 1, 2, or 3; each of R⁸, and R⁹ are        independently selected from the group consisting of hydrogen,        C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀ cycloalkyl, C₅₋₂₀cycloalkenyl,        C₆₋₂₀cycloalkenylalkyl, C₆₋₁₂aryl, aminoC₁₋₆alkyl, and        C₇-C₂₀arylalkyl; or R⁸ and R⁹ together with the atom to which        they are attached form a C₃₋₂₀cycloalkyl, C₅₋₂₀cycloalkenyl or        heterocyclyl; preferably L¹ is SiR⁸R⁹; each of R⁸, and R⁹ are        independently selected from the group consisting of hydrogen,        C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀ cycloalkyl, C₅₋₂₀cycloalkenyl,        C₆₋₂₀cycloalkenylalkyl, C₆₋₁₂aryl, aminoC₁₋₆alkyl, and        C₇-C₂₀arylalkyl; or R⁸ and R⁹ together with the atom to which        they are attached form a C₃₋₂₀cycloalkyl, C₅₋₂₀cycloalkenyl or        heterocyclyl; preferably each of R⁸, and R⁹ are independently        selected from the group consisting of C₁₋₆alkyl;    -   M¹ is a transition metal selected from the group consisting of        zirconium, titanium, hafnium, and vanadium; and preferably is        zirconium; and    -   Q¹ and Q² are each independently selected from the group        consisting of halogen, C₁₋₂₀alkyl, —N(R¹¹)₂, C₁₋₂₀alkoxy,        C₃₋₂₀cycloalkoxy, C₇₋₂₀aralkoxy, C₃₋₂₀cycloalkyl, C₆₋₂₀aryl,        C₇₋₂₀alkylaryl, C₇₋₂₀aralkyl, and heteroC₁₋₂₀alkyl; wherein R¹¹        is hydrogen or C₁₋₂₀alkyl.

-   21. The composition according to any one of statements 1-20, wherein    catalyst component B comprises a bridged metallocene catalyst of    formula (II), wherein

-   -   each of R⁵, R⁶, and R⁷, are independently selected from the        group consisting of C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀cycloalkyl,        C₅₋₂₀cycloalkenyl, C₆₋₂₀cycloalkenylalkyl, C₆₋₂₀aryl,        C₁₋₂₀alkoxy, C₇₋₂₀alkylaryl, C₇₋₂₀arylalkyl, halogen, Si(R¹⁰)₃,        and heteroC₁₋₂₀alkyl; wherein each R¹⁰ is independently        hydrogen, C₁₋₂₀alkyl, or C₃₋₂₀alkenyl; and r, s, t are each        independently an integer selected from 0, 1, 2, 3, or 4;    -   L² is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an        integer selected from 1, 2, or 3; each of R⁸, and R⁹ are        independently selected from the group consisting of hydrogen,        C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀ cycloalkyl, C₅₋₂₀cycloalkenyl,        C₅₋₂₀cycloalkenylalkyl, C₆₋₁₂aryl, aminoC₁₋₆alkyl, and        C₇-C₂₀arylalkyl; or R⁸ and R⁹ together with the atom to which        they are attached form a C₃₋₂₀cycloalkyl, C₅₋₂₀cycloalkenyl or        heterocyclyl;    -   M² is a transition metal selected from the group consisting of        zirconium, titanium, hafnium, and vanadium; and preferably is        zirconium; and    -   Q³ and Q⁴ are each independently selected from the group        consisting of halogen, C₁₋₂₀alkyl, —N(R¹¹)₂, C₁₋₂₀alkoxy,        C₃₋₂₀cycloalkoxy, C₇₋₂₀aralkoxy, C₃₋₂₀cycloalkyl, C₆₋₂₀aryl,        C₇₋₂₀alkylaryl, C₇₋₂₀aralkyl, and heteroC₁₋₂₀alkyl; wherein R¹¹        is hydrogen or C₁₋₂₀alkyl.

-   22. The composition according to any one of statements 17-21,    wherein    -   each of R¹, and R³ are independently selected from the group        consisting of C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl,        C₅₋₈cycloalkenyl, C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, C₁₋₈alkoxy,        C₇₋₁₂ alkylaryl, C₇₋₁₂arylalkyl, halogen, Si(R¹⁰)₃, and        heteroC₁₋₈alkyl; wherein at least one of R¹ or R³ is C₆₋₁₂aryl,        preferably phenyl; wherein each R¹⁰ is independently hydrogen,        C₁₋₈alkyl, or C₃₋₈alkenyl; and m, n, p, q are each independently        an integer selected from 0, 1, 2, 3, or 4;    -   each of R², and R⁴, are independently selected from the group        consisting of C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl,        C₅₋₈cycloalkenyl, C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, C₁₋₈alkoxy,        C₇₋₁₂ alkylaryl, C₇₋₁₂arylalkyl, halogen, Si(R¹⁰)₃, and        heteroC₁₋₈alkyl; wherein at least one of R² or R² is C₆₋₁₂aryl,        preferably phenyl; wherein each R¹⁰ is independently hydrogen,        C₁₋₈alkyl, or C₃₋₈alkenyl; and m, n, p, q are each independently        an integer selected from 0, 1, 2, 3, or 4;    -   L¹ is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an        integer selected from 1, 2, or 3; each of R⁸, and R⁹ are        independently selected from the group consisting of hydrogen,        C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl,        C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, aminoC₁₋₆alkyl, and        C₇-C₁₂arylalkyl; or R⁸ and R⁹ together with the atom to which        they are attached form a C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl or        heterocyclyl; preferably L¹ is SiR⁸R⁹; preferably each of R⁸,        and R⁹ are independently selected from the group consisting of        hydrogen, or C₁₋₈alkyl;    -   M¹ is a transition metal selected from the group consisting of        zirconium, titanium, hafnium, and vanadium; and preferably is        zirconium; and    -   Q¹ and Q² are each independently selected from the group        consisting of halogen, C₁₋₈alkyl, —N(R¹¹)₂, C₁₋₈alkoxy,        C₃₋₈cycloalkoxy, C₇₋₁₂aralkoxy, C₃₋₈cycloalkyl, C₆₋₁₂aryl,        C₇₋₁₂alkylaryl, C₇₋₁₂aralkyl, and heteroC₁₋₈alkyl; wherein R¹¹        is hydrogen or C₁₋₈alkyl.

-   23. The composition according to any one of statements 17-22,    wherein    -   each of R⁵, R⁶, and R⁷, are independently selected from the        group consisting of C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl,        C₅₋₈cycloalkenyl, C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, C₁₋₈alkoxy,        C₇₋₁₂alkylaryl, C₇₋₁₂arylalkyl, halogen, Si(R¹⁰)₃, and        heteroC₁₋₈alkyl; wherein each R¹⁰ is independently hydrogen,        C₁₋₈alkyl, or C₃₋₈alkenyl; and r, s, t are each independently an        integer selected from 0, 1, 2, 3, or 4;    -   L² is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR³; wherein h is an        integer selected from 1, 2, or 3; each of R⁸, and R⁹ are        independently selected from the group consisting of hydrogen,        C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl,        C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, aminoC₁₋₆alkyl, and        C₇-C₁₂arylalkyl; or R³ and R⁹ together with the atom to which        they are attached form a C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl or        heterocyclyl;    -   M² is a transition metal selected from the group consisting of        zirconium, titanium, hafnium, and vanadium; and preferably is        zirconium; and    -   Q³ and Q⁴ are each independently selected from the group        consisting of halogen, C₁₋₈alkyl, —N(R¹¹)₂, C₁₋₈alkoxy,        C₃₋₈cycloalkoxy, C₇₋₁₂aralkoxy, C₃₋₈cycloalkyl, C₆₋₁₂aryl,        C₇₋₁₂alkylaryl, C₇₋₁₂aralkyl, and heteroC₁₋₈alkyl; wherein R¹¹        is hydrogen or C₁₋₈alkyl.

-   24. The composition according to any one of statements 17-23,    wherein    -   each of R¹, and R³ are independently selected from the group        consisting of C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₆₋₁₂aryl,        and halogen; wherein at least one of R¹ or R³ is C₆₋₁₂aryl,        preferably phenyl; and m, n, p, q are each independently an        integer selected from 0, 1, 2, 3, or 4; preferably 0, 1, 2, or        3, preferably 0, 1, or 2; preferably 0, or 1;    -   each of R², and R⁴, are independently selected from the group        consisting of C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₆₋₁₂aryl,        and halogen; wherein at least one of R² or R² is C₆₋₁₂aryl,        preferably phenyl; and m, n, p, q are each independently an        integer selected from 0, 1, 2, 3, or 4; preferably 0, 1, 2, or        3, preferably 0, 1, or 2; preferably 0, or 1;    -   L¹ is —[CR⁸R⁹]_(h)—, or SiR⁸R⁹; wherein h is an integer selected        from 1, or 2; each of R⁸, and R⁹ are independently selected from        the group consisting of hydrogen, C₁₋₈alkyl, C₃₋₈alkenyl,        C₃₋₈cycloalkyl; C₅₋₈cycloalkenyl, C₆₋₈cycloalkenylalkyl, and        C₆₋₁₂aryl; preferably L¹ is SiR⁸R⁹; preferably each of R⁸, and        R⁹ are independently selected from the group consisting of        hydrogen, or C₁₋₈alkyl;    -   M¹ is a transition metal selected from zirconium, or hafnium;        and preferably zirconium; and    -   Q¹ and Q² are each independently selected from the group        consisting of halogen, C₁₋₈alkyl, —N(R¹¹)₂, C₆₋₁₂aryl, and        C₇₋₁₂aralkyl; wherein R¹¹ is hydrogen or C₁₋₈alkyl, preferably        Q¹ and Q² are each independently selected from the group        consisting of C, F, Br, I, methyl, benzyl, and phenyl.

-   25. The composition according to any one of statements 17-24,    wherein    -   each of R⁵, R⁶, and R⁷, is independently selected from the group        consisting of C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₆₋₁₂aryl,        and halogen; and r, s, t are each independently an integer        selected from 0, 1, 2, 3, or 4; preferably 0, 1, 2, or 3,        preferably 0, 1, or 2; preferably 0, or 1;    -   L² is —[CR⁸R⁹]_(h)—, or SiR⁸R⁹; wherein h is an integer selected        from 1, or 2; each of R³, and R⁹ are independently selected from        the group consisting of hydrogen, C₁₋₈alkyl, C₃₋₈alkenyl,        C₃₋₈cycloalkyl; C₅₋₈cycloalkenyl, C₆₋₈cycloalkenylalkyl, and        C₆₋₁₂aryl;    -   M² is a transition metal selected from zirconium, or hafnium;        and preferably zirconium; and    -   Q³ and Q⁴ are each independently selected from the group        consisting of halogen, C₁₋₈alkyl, —N(R¹¹)₂, C₆₋₁₂aryl, and        C₇₋₁₂aralkyl; wherein R¹¹ is hydrogen or C₁₋₈alkyl, preferably        Q¹ and Q² are each independently selected from the group        consisting of C, F, Br, I, methyl, benzyl, and phenyl.

-   26. An olefin polymerization process, the process comprising:    contacting a catalyst composition according to any one of statements    1-25, with an olefin monomer, optionally hydrogen, and optionally    one or more olefin co-monomers; and polymerizing the monomer, and    the optionally one or more olefin co-monomers, in the presence of    the at least one catalyst composition, and optional hydrogen,    thereby obtaining a polyolefin.

-   27. The process according to statement 26, wherein the process is    conducted in one or more batch reactors, slurry reactors, gas-phase    reactors, solution reactors, high pressure reactors, tubular    reactors, autoclave reactors, or a combination thereof.

-   28. The process according to any one of statements 26-27, wherein    the olefin monomer is ethylene, and the olefin comonomer comprises    propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,    1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,    1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene,    3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

-   29. The process according to any one of statements 26-27, wherein    the olefin monomer is propylene, and the olefin comonomer comprises    ethylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,    1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,    1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene,    3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

-   30. An olefin polymer at least partially catalyzed by at least one    catalyst composition according to any one of statements 1-25, or    produced by the process according to any one of statements 26-29.

-   31. Olefin polymer according to statement 30, wherein said olefin    polymer is polyethylene.

-   32. Olefin polymer according to statement 30, wherein said olefin    polymer is polypropylene.

-   33. An article comprising the olefin polymer according to any one of    statements 30-32.

The present invention provides a catalyst composition comprising

catalyst component A comprising a bridged metallocene compound with twogroups independently selected from indenyl or tetrahydroindenyl, eachgroup being unsubstituted or substituted; preferably catalyst componentA comprises a bridged metallocene compound with two indenyl groups, eachindenyl being substituted with one or more substituents, wherein atleast one of the substituent is an aryl, preferably a phenyl; whereinsaid aryl may be unsubstituted or substituted; preferably wherein thearyl, preferably the phenyl is on the 3-position on each indenyl;

catalyst component B comprising a bridged metallocene compound with asubstituted or unsubstituted cyclopentadienyl group and a substituted orunsubstituted fluorenyl group;

an optional activator; an optional support; and an optional co-catalyst.

As used herein, the term “catalyst” refers to a substance that causes achange in the rate of a reaction. In the present invention, it isespecially applicable to catalysts suitable for a polymerization,preferably for the polymerization of olefins to polyolefins.

The term “metallocene catalyst” is used herein to describe anytransition metal complexes comprising metal atoms bonded to one or moreligands. The metallocene catalysts are compounds of Group IV transitionmetals of the Periodic Table such as titanium, zirconium, hafnium, etc.,and have a coordinated structure with a metal compound and ligandscomposed of one or two groups of cyclopentadienyl, indenyl,tetrahydroindenyl, fluorenyl or their derivatives. Metallocenes comprisea single metal site, which allows for more control of branching andmolecular weight distribution of the polymer. Monomers are insertedbetween the metal and the growing chain of polymer. Specifically forthis invention the catalyst needs to be a “bridged metallocenecatalyst”.

In one embodiment, the bridged metallocene catalyst can be representedby formula (III) for catalyst A, and formula (IV) for catalyst B:wherein

L¹(Ar¹)₂M¹Q¹Q²  (III),

L²(Ar²)(Ar³)M²Q3Q⁴  (IV),

each Ar¹ is independently indenyl or tetrahydroindenyl, optionallysubstituted with one or more substituents each independently selectedfrom the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkoxy,alkylaryl, arylalkyl, halogen, Si(R¹⁰)₃, heteroalkyl; wherein each R¹⁰is independently hydrogen, alkyl, or alkenyl. Each indenyl ortetrahydroindenyl component may be substituted in the same way ordifferently from one another at one or more positions of either of thefused rings. Each substituent can be independently chosen. Preferably,each Ar¹ is indenyl, each indenyl being independently substituted withone or more substituents, wherein at least one of the substituent is anaryl or heteroaryl; preferably wherein the aryl or heteroarylsubstituent is on the 3-position on each indenyl, wherein Ar1 can befurther substituted with one or more substituents each independentlyselected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl,alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)₃, heteroalkyl; whereineach R¹⁰ is independently hydrogen, alkyl, or alkenyl;

Ar² is cyclopentadienyl, optionally substituted with one or moresubstituents each independently selected from the group consisting ofalkyl, alkenyl, cycloalkyl, cycloalkenyl, or cycloalkenylalkyl, aryl,alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)₃, heteroalkyl; whereineach R¹⁰ is independently hydrogen, alkyl, or alkenyl;

Ar³ is fluorenyl, optionally substituted with one or more substituentseach independently selected from the group consisting of alkyl, alkenyl,cycloalkyl, cycloalkenyl, or cycloalkenylalkyl, aryl, alkoxy, alkylaryl,arylalkyl, halogen, Si(R¹⁰)₃, heteroalkyl; wherein each R¹⁰ isindependently hydrogen, alkyl, or alkenyl;

each of M¹ and M² is a transition metal selected from the groupconsisting of zirconium, hafnium, titanium, and vanadium; and preferablyis zirconium;

Q¹ and Q² are each independently selected from the group consisting ofhalogen, alkyl, —N(R¹¹)₂, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl,aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R¹¹ is hydrogen oralkyl;

Q³ and Q⁴ are each independently selected from the group consisting ofhalogen, alkyl, —N(R¹¹)₂, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl,aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R¹¹ is hydrogen oralkyl;

L¹ is a divalent group or moiety bridging the two Ar¹ groups, preferablyselected from —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is aninteger selected from 1, 2, or 3; each of R⁸, and R⁹ are independentlyselected from the group consisting of hydrogen, alkyl, alkenyl,cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, andarylalkyl; or R⁸ and R⁹ together with the atom to which they areattached form a cycloalkyl, cycloalkenyl or heterocyclyl; preferably L¹is SiR⁸R⁹;

L² is a divalent group or moiety bridging Ar² and Ar³ groups, preferablyselected from —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is aninteger selected from 1, 2, or 3; each of R⁸, and R⁹ are independentlyselected from the group consisting of hydrogen, alkyl, alkenyl,cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, andarylalkyl; or R⁸ and R⁹ together with the atom to which they areattached form a cycloalkyl, cycloalkenyl or heterocyclyl.

In some embodiments, each Ar¹ is indenyl, each indenyl beingindependently substituted with one or more substituents, wherein atleast one of the substituent is an aryl or heteroaryl; preferablywherein the aryl or heteroaryl substituent is on the 3-position on eachindenyl; each indenyl being further optionally substituted with one ormore substituents each independently selected from the group consistingof C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀cycloalkyl, C₅₋₂₀cycloalkenyl,C₈₋₂₀cycloalkenylalkyl, C₈₋₂₀aryl, C₁₋₂₀alkoxy, C₇₋₂₀alkylaryl,C₇₋₂₀arylalkyl, halogen, Si(R¹⁰)₃, and heteroC₁₋₁₂alkyl; wherein eachR¹⁰ is independently hydrogen, C₁₋₂₀alkyl, or C₃₋₂₀alkenyl. Preferablyeach Ar¹ is indenyl, each indenyl being independently substituted withone or more substituents, wherein at least one of the substituent is anC₆₋₁₂aryl; preferably wherein the C₆₋₁₂aryl substituent is on the3-position on each indenyl; each indenyl being further optionallysubstituted with one or more substituents each independently selectedfrom the group consisting of C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl,C₅₋₈cycloalkenyl, C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, C₁₋₈alkoxy,C₇₋₁₂alkylaryl, C₇₋₁₂arylalkyl, halogen, Si(R¹⁰)₃, and heteroC₁₋₈alkyl;wherein each R¹⁰ is independently hydrogen, C₁₋₈alkyl, or C₃₋₈alkenyl.Preferably each Ar¹ is indenyl, each indenyl being independentlysubstituted with one or more substituents, wherein at least one of thesubstituent is an C₆₋₁₂aryl; preferably wherein the C₆₋₁₂arylsubstituent is on the 3-position on each indenyl; each indenyl beingfurther optionally substituted with one or more substituents eachindependently selected from the group consisting of C₁₋₈alkyl,C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₆₋₁₂aryl, and halogen.

In some embodiments, Ar² is cyclopentadienyl, optionally substitutedwith one or more substituents each independently selected from the groupconsisting of C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀cycloalkyl,C₅₋₂₀cycloalkenyl, C₆₋₂₀cycloalkenylalkyl, C₆₋₂₀aryl, C₁₋₂₀alkoxy,C₇₋₂₀alkylaryl, C₇₋₂₀arylalkyl, halogen, Si(R¹⁰)₃, and heteroC₁₋₁₂alkyl;wherein each R¹⁰ is independently hydrogen, C₁₋₂₀alkyl, or C₃₋₂₀alkenyl.Preferably Ar² is cyclopentadienyl, optionally substituted with one ormore substituents each independently selected from the group consistingof C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl,C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, C₁₋₈alkoxy, C₇₋₁₂alkylaryl,C₇₋₁₂arylalkyl, halogen, Si(R¹⁰)₃, and heteroC₁₋₈alkyl; wherein each R¹⁰is independently hydrogen, C₁₋₈alkyl, or C₃₋₈alkenyl. Preferably Ar² iscyclopentadienyl, optionally substituted with one or more substituentseach independently selected from the group consisting of C₁₋₈alkyl,C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₆₋₁₂aryl, and halogen.

In some embodiments, Ar³ is fluorenyl, optionally substituted with oneor more substituents each independently selected from the groupconsisting of C₁₋₂₀alkyl, C₃₋₂₀ alkenyl, C₃₋₂₀cycloalkyl,C₅₋₂₀cycloalkenyl, C₆₋₂₀cycloalkenylalkyl, C₆₋₂₀aryl, C₁₋₂₀alkoxy,C₇₋₂₀alkylaryl, C₇₋₂₀arylalkyl, halogen, Si(R¹⁰)₃, and heteroC₁₋₁₂alkyl;wherein each R¹⁰ is independently hydrogen, C₁₋₂₀alkyl, or C₃₋₂₀alkenyl.Preferably Ar² is fluorenyl, optionally substituted with one or moresubstituents each independently selected from the group consisting ofC₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl,C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, C₁₋₈alkoxy, C₇₋₁₂ alkylaryl,C₇₋₁₂arylalkyl, halogen, Si(R¹⁰)₃, and heteroC₁₋₈alkyl; wherein each R¹⁰is independently hydrogen, C₁₋₈alkyl, or C₃₋₈alkenyl. Preferably, Ar³ isfluorenyl, optionally substituted with one or more substituents eachindependently selected from the group consisting of C₁₋₈alkyl,C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₆₋₁₂aryl, and halogen.

In some embodiments, L¹ is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸;wherein h is an integer selected from 1, 2, or 3; each of R⁸, and R⁹ areindependently selected from the group consisting of hydrogen,C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀cycloalkyl, C₅₋₂₀cycloalkenyl,C₆₋₂₀cycloalkenylalkyl, C₆₋₁₂aryl, and C₇-C₂₀arylalkyl; or R⁸ and R⁹together with the atom to which they are attached form aC₃₋₂₀cycloalkyl, C₅₋₂₀cycloalkenyl or heterocyclyl. Preferably L¹ is—[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selectedfrom 1, 2, or 3; each of R⁸, and R⁹ are independently selected from thegroup consisting of hydrogen, C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl,C₅₋₈cycloalkenyl, C₆₋₈cycloalkenylalkyl, C₆₋₁₂aryl, and C₇-C₁₂arylalkyl;or R³ and R⁹ together with the atom to which they are attached form aC₃₋₈cycloalkyl, C₅₋₈cycloalkenyl or heterocyclyl. Preferably, L¹ is—[CR⁸R⁹]_(h)—, or SiR⁸R⁹; wherein h is an integer selected from 1, or 2;each of R⁸, and R⁹ are independently selected from the group consistingof hydrogen, C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl,C₆₋₈cycloalkenylalkyl, and C₆₋₁₂aryl. Preferably, L¹ is SiR⁸R⁹; each ofR⁸, and R⁹ are independently selected from the group consisting ofhydrogen, C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl,C₆₋₈cycloalkenylalkyl, and C₆₋₁₂aryl; preferably C₁₋₈alkyl.

In some embodiments, Q¹ and Q² are each independently selected from thegroup consisting of halogen, C₁₋₂₀alkyl, —N(R¹¹)₂, C₁₋₂₀alkoxy,C₃₋₂₀cycloalkoxy, C₇₋₂₀aralkoxy, C₃₋₂₀cycloalkyl, C₆₋₂₀aryl,C₇₋₂₀alkylaryl, C₇₋₂₀aralkyl, and heteroC₁₋₂₀alkyl; wherein R¹¹ ishydrogen or C₁₋₂₀alkyl. Preferably Q¹ and Q² are each independentlyselected from the group consisting of halogen, C₁₋₈alkyl, —N(R¹¹)₂,C₁₋₈alkoxy, C₃₋₈cycloalkoxy, C₇₋₁₂aralkoxy, C₃₋₈cycloalkyl, C₆₋₁₂aryl,C₇₋₁₂alkylaryl, C₇₋₁₂aralkyl, and heteroC₁₋₈alkyl; wherein R¹¹ ishydrogen or C₁₋₈alkyl. Preferably, Q¹ and Q² are each independentlyselected from the group consisting of halogen, C₁₋₈alkyl, —N(R¹¹)₂,C₆₋₁₂aryl, and C₇₋₁₂aralkyl; wherein R¹¹ is hydrogen or C₁₋₈alkyl,preferably Q¹ and Q² are each independently selected from the groupconsisting of Cl, F, Br, I, methyl, benzyl, and phenyl.

In some embodiments, L² is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸;wherein h is an integer selected from 1, 2, or 3; each of R⁸, and R⁹ areindependently selected from the group consisting of hydrogen, C₁₋₂₀alkyl, C₃₋₂₀alkenyl, C₃₋₂₀cycloalkyl, C₅₋₂₀cycloalkenyl,C₆₋₂₀cycloalkenylalkyl, C₆₋₁₂aryl, and C₇-C₂₀arylalkyl; or R⁸ and R⁹together with the atom to which they are attached form aC₃₋₂₀cycloalkyl, C₅₋₂₀cycloalkenyl or heterocyclyl. Preferably L² is—[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selectedfrom 1, 2, or 3; each of R⁸, and R⁹ are independently selected from thegroup consisting of hydrogen, C₁₋₈alkyl, C₃₋₈ alkenyl, C₃₋₈cycloalkyl,C₅₋₈cycloalkenyl, C₆₋₈cycloalkenylalkyl, C₈₋₁₂aryl, and C₇-C₁₂arylalkyl;or R⁸ and R⁹ together with the atom to which they are attached form aC₃₋₈cycloalkyl, C₅₋₈cycloalkenyl or heterocyclyl. Preferably, L² is—[CR⁸R⁹]_(h)—, or SiR⁸R⁹; wherein h is an integer selected from 1, or 2;each of R⁸, and R⁹ are independently selected from the group consistingof hydrogen, C₁₋₈alkyl, C₃₋₈alkenyl, C₃₋₈cycloalkyl, C₅₋₈cycloalkenyl,C₆₋₈cycloalkenylalkyl, and C₆₋₁₂aryl.

In some embodiments, Q³ and Q⁴ are each independently selected from thegroup consisting of halogen, C₁₋₂₀ alkyl, —N(R¹¹)₂, C₁₋₂₀alkoxy,C₃₋₂₀cycloalkoxy, C₇₋₂₀aralkoxy, C₃₋₂₀cycloalkyl, C₆₋₂₀aryl,C₇₋₂₀alkylaryl, C₇₋₂₀aralkyl, and heteroC₁₋₂₀alkyl; wherein R¹¹ ishydrogen or C₁₋₂₀alkyl. Preferably Q³ and Q⁴ are each independentlyselected from the group consisting of halogen, C₁₋₈alkyl, —N(R¹¹)₂,C₁₋₈alkoxy, C₃₋₈cycloalkoxy, C₇₋₁₂aralkoxy, C₃₋₈cycloalkyl, C₆₋₁₂aryl,C₇₋₁₂ alkylaryl, C₇₋₁₂aralkyl, and heteroC₁₋₈alkyl; wherein R¹¹ ishydrogen or C₁₋₈alkyl. Preferably, Q³ and Q⁴ are each independentlyselected from the group consisting of halogen, C₁₋₈alkyl, —N(R¹¹)₂,C₆₋₁₂aryl, and C₇₋₁₂aralkyl; wherein R¹¹ is hydrogen or C₁₋₈alkyl,preferably Q¹ and Q² are each independently selected from the groupconsisting of Cl, F, Br, I, methyl, benzyl, and phenyl.

In some preferred embodiments, catalyst component A comprises a bridgedmetallocene catalyst of formula (1I), more preferably catalyst componentA comprises a bridged metallocene catalyst of formula (I); wherein

each dotted line represents an optional double bond

wherein each of R¹, R² R³ and R⁴, m, n, p, q, L¹, M¹, Q¹ and Q² have thesame meaning as that defined herein above and in the statements.

A bridged metallocene catalyst component can appear in twostereo-isomeric forms: a racemic form and a meso form. In some preferredembodiments, catalyst component A is a meso bridged bis-indenylmetallocene compound, preferably of formula (I).

In some preferred embodiments, catalyst component B comprises a bridgedmetallocene catalyst of formula (II),

wherein each of R⁵, R⁶, R⁷, r, s, t, L², M², Q³ and Q⁴ have the samemeaning as that defined herein above and in the statements.

Non-Limiting Examples of Catalyst A are Shown Below

Preferred Examples of Catalyst A are Shown Below

Non-Limiting Examples of Catalyst B are Shown Below

The bridged metallocene catalysts for the composition herein arepreferably provided on a solid support.

The support can be an inert organic or inorganic solid, which ischemically unreactive with any of the components of the conventionalbridged metallocene catalyst. Suitable support materials for thesupported catalyst include solid inorganic oxides, such as silica,alumina, magnesium oxide, titanium oxide, thorium oxide, as well asmixed oxides of silica and one or more Group 2 or 13 metal oxides, suchas silica-magnesia and silica-alumina mixed oxides. Silica, alumina, andmixed oxides of silica and one or more Group 2 or 13 metal oxides arepreferred support materials. Preferred examples of such mixed oxides arethe silica-aluminas. For example the solid oxide comprises titanatedsilica, silica, alumina, silica-alumina, silica-coated alumina, aluminumphosphate, aluminophosphate, heteropolytungstate, titania, zirconia,magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixturethereof, preferably silica, titanated silica, silica treated withfluoride, silica-alumina, alumina treated with fluoride, sulfatedalumina, silica-alumina treated with fluoride, sulfated silica-alumina,silica-coated alumina, silica treated with fluoride, sulfatedsilica-coated alumina, or any combination thereof. Most preferred is atitanated silica, or a silica compound. In a preferred embodiment, thebridged metallocene catalysts are provided on a solid support,preferably a titanated silica, or a silica support. The silica may be ingranular, agglomerated, fumed or other form.

In some embodiments, the support of the bridged metallocene catalysts isa porous support, and preferably a porous titanated silica, or silicasupport having a surface area comprised between 200 and 900 m²/g. Inanother embodiment, the support of the polymerization catalyst is aporous support, and preferably a porous titanated silica, or silicasupport having an average pore volume comprised between 0.5 and 4 ml/g.In yet another embodiment, the support of the polymerization catalyst isa porous support, and preferably a porous titanated silica, or silicasupport having an average pore diameter comprised between 50 and 300 Å,and preferably between 75 and 220 Å.

In some embodiments, the support has a D50 of at most 150 μm, preferablyof at most 100 μm, preferably of at most 75 μm, preferably of at most 50μm, preferably of at most 40 μm, preferably of at most 30 μm. The D50 isdefined as the particle size for which fifty percent by weight of theparticles has a size lower than the D50. The measurement of the particlesize can be made according to the International Standard ISO 13320:2009(“Particle size analysis-Laser diffraction methods”). For example, theD50 can be measured by sieving, by BET surface measurement, or by laserdiffraction analysis. For example, Malvern Instruments' laserdiffraction systems may advantageously be used. The particle size may bemeasured by laser diffraction analysis on a Malvern type analyzer. Theparticle size may be measured by laser diffraction analysis on a Malverntype analyzer after having put the supported catalyst in suspension incyclohexane. Suitable Malvern systems include the Malvern 2000, MalvernMasterSizer (such as Mastersizer S), Malvern 2600 and Malvern 3600series. Such instruments together with their operating manual meet oreven exceed the requirements set-out within the ISO 13320 Standard. TheMalvern MasterSizer (such as Mastersizer S) may also be useful as it canmore accurately measure the D50 towards the lower end of the range e.g.for average particle sizes of less 8 μm, by applying the theory of Mie,using appropriate optical means.

Preferably, the bridged metallocene catalyst is activated by anactivator. The activator can be any activator known for this purposesuch as an aluminum-containing activator, a boron-containing activator,or a fluorinated activator. The aluminum-containing activator maycomprise an alumoxane, an alkyl aluminum, a Lewis acid and/or afluorinated catalytic support.

In some embodiments, alumoxane is used as an activator for the bridgedmetallocene catalyst.

The alumoxane can be used in conjunction with a catalyst in order toimprove the activity of the catalyst during the polymerization reaction.

As used herein, the term “alumoxane” and “aluminoxane” are usedinterchangeably, and refer to a substance, which is capable ofactivating the bridged metallocene catalyst. In some embodiments,alumoxanes comprise oligomeric linear and/or cyclic alkyl alumoxanes. Ina further embodiment, the alumoxane has formula (V) or (VI)

R^(a)—(Al(R^(a))—O)_(x)—AlR^(a) ₂  (V) for oligomeric, linearalumoxanes; or

(—Al(R^(a))—O—)_(y)  (VI) for oligomeric, cyclic alumoxanes

wherein x is 1-40, and preferably 10-20;

wherein y is 3-40, and preferably 3-20; and

wherein each R^(a) is independently selected from a C₁₋₈alkyl, andpreferably is methyl. In a preferred embodiment, the alumoxane ismethylalumoxane (MAO).

The composition may comprise a co-catalyst. One or more aluminumalkylrepresented by the formula AlR^(b) _(x) can be used as additionalco-catalyst, wherein each R^(b) is the same or different and is selectedfrom halogens or from alkoxy or alkyl groups having from 1 to 12 carbonatoms and x is from 1 to 3. Non-limiting examples are Tri-Ethyl Aluminum(TEAL), Tri-Iso-Butyl Aluminum (TIBAL), Tri-Methyl Aluminum (TMA), andMethyl-Methyl-Ethyl Aluminum (MMEAL). Especially suitable aretrialkylaluminums, the most preferred being triisobutylaluminum (TIBAL)and triethylaluminum (TEAL).

In a preferred embodiment, the weight ratio of catalyst component A tocatalyst component B is in a range of from 1:9 to 9:1, preferably, 1:5to 5:1, preferably 1:4 to 4:1.

The catalyst composition can be particularly useful in a process for thepreparation of a polymer comprising contacting at least one monomer withat least one catalyst composition. Preferably, said polymer is apolyolefin, preferably said monomer is an alpha-olefin.

The catalyst composition of the present invention is thereforeparticularly suitable for being used in the preparation of a polyolefin.The present invention also relates to the use of a catalyst compositionin olefin polymerization.

The present invention also encompasses an olefin polymerization process,the process comprising: contacting a catalyst composition according tothe invention, with an olefin monomer, optionally hydrogen, andoptionally one or more olefin co-monomers; and polymerizing the monomer,and the optionally one or more olefin co-monomers, in the presence ofthe at least one catalyst composition, and optional hydrogen, therebyobtaining a polyolefin.

The term “olefin” refers herein to molecules composed of carbon andhydrogen, containing at least one carbon-carbon double bond. Olefinscontaining one carbon-carbon double bond are denoted herein asmono-unsaturated hydrocarbons and have the chemical formula C_(n)H_(2n),where n equals at least two. “Alpha-olefins”, “α-olefins”, “1-alkenes”or “terminal olefins” are used as synonyms herein and denote olefins oralkenes having a double bond at the primary or alpha (α) position.

Throughout the present application the terms “olefin polymer”,“polyolefin” and “polyolefin polymer” may be used synonymously.

Suitable polymerization includes but is not limited tohomopolymerization of an alpha-olefin, or copolymerization of thealpha-olefin and at least one other alpha-olefin comonomer.

As used herein, the term “comonomer” refers to olefin co-monomers whichare suitable for being polymerized with alpha-olefin monomer. Thecomonomer if present is different from the olefin monomer and chosensuch that it is suited for copolymerization with the olefin monomer.Co-monomers may comprise but are not limited to aliphatic C₂-C₂₀alpha-olefins. Examples of suitable aliphatic C₃-C₂₀ alpha-olefinsinclude ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, and 1-eicosene. Further examples of suitable comonomersare vinyl acetate (H₃C—C(═O)O—CH═CH₂) or vinyl alcohol (“HO—CH═CH₂”).Examples of olefin copolymers suited which can be prepared can be randomcopolymers of propylene and ethylene, random copolymers of propylene and1-butene, heterophasic copolymers of propylene and ethylene,ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octenecopolymers, copolymers of ethylene and vinyl acetate (EVA), copolymersof ethylene and vinyl alcohol (EVOH).

In some embodiments, the olefin monomer is ethylene, and the olefincomonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene,isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene,2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

In some embodiments, the olefin monomer is propylene, and the olefincomonomer comprises ethylene, 1-butene, 2-butene, 3-methyl-1-butene,isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene,2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

The polyolefin can be prepared out in bulk, gas, solution and/or slurryphase. The process can be conducted in one or more batch reactors,slurry reactors, gas-phase reactors, solution reactors, high pressurereactors, tubular reactors, autoclave reactors, or a combinationthereof.

The term “slurry” or “polymerization slurry” or “polymer slurry”, asused herein refers to substantially a multi-phase composition includingat least polymer solids and a liquid phase, the liquid phase being thecontinuous phase. The solids may include the catalyst and polymerizedmonomer.

In some embodiments, the liquid phase comprises a diluent. As usedherein, the term “diluent” refers to any organic diluent, which does notdissolve the synthesized polyolefin. As used herein, the term “diluent”refers to diluents in a liquid state, liquid at room temperature andpreferably liquid under the pressure conditions in the loop reactor.Suitable diluents comprise but are not limited to hydrocarbon diluentssuch as aliphatic, cycloaliphatic and aromatic hydrocarbon solvents, orhalogenated versions of such solvents. Preferred solvents are C₁₂ orlower, straight chain or branched chain, saturated hydrocarbons, C to Csaturated alicyclic or aromatic hydrocarbons or C₂ to C₆ halogenatedhydrocarbons. Non-limiting illustrative examples of solvents are butane,isobutane, pentane, hexane, heptane, cyclopentane, cyclohexane,cycloheptane, methyl cyclopentane, methyl cyclohexane, isooctane,benzene, toluene, xylene, chloroform, chlorobenzenes,tetrachloroethylene, dichloroethane and trichloroethane, preferablyisobutane or hexane.

The polymerization can also be performed in gas phase, under gas phaseconditions. The term “gas phase conditions” as used herein refers totemperatures and pressures suitable for polymerizing one or more gaseousphase olefins to produce polymer therefrom.

The polymerization steps can be performed over a wide temperature range.In certain embodiments, the polymerization steps may be performed at atemperature from 20° C. to 125° C., preferably from 60° C. to 110° C.,more preferably from 75° C. to 100° C. and most preferably from 78° C.to 98° C. Preferably, the temperature range may be within the range from75° C. to 100° C. and most preferably from 78° C. to 98° C. Saidtemperature may fall under the more general term of polymerizationconditions.

In certain embodiments, in slurry conditions, the polymerization stepsmay be performed at a pressure from about 20 bar to about 100 bar,preferably from about 30 bar to about 50 bar, and more preferably fromabout 37 bar to about 45 bar. Said pressure may fall under the moregeneral term of polymerization conditions.

The invention also encompasses a polymer at least partially catalyzed byat least one composition according to the invention or produced by aprocess according to the invention.

The present invention also encompasses a polymer, preferably an olefinpolymer produced by a process as defined herein. In some embodiments,said olefin polymer is polyethylene. In some embodiments, said olefinpolymer is polypropylene.

After the polymer is produced, it may be formed into various articles,including but not limited to, film products, caps and closures,rotomoulding, grass yarn, etc.

The present invention therefore also encompasses an article comprising apolymer as defined herein; preferably a polyolefin as defined herein, orobtained according to a process as defined herein. In some embodiments,said article is film products, caps and closures, rotomoulding, grassyarn, pipes, etc.

The invention will now be illustrated by the following, non-limitingillustrations of particular embodiments of the invention.

EXAMPLES

Test Methods

The density of the polyolefin was measured according to the method ofstandard ISO 1183-1:2012 method A at a temperature of 23° C.

The melt flow rate MI2 was measured according to ISO 1133:1997,condition D, at 190° C. and under a load of 2.16 kg.

The molecular weight (M_(n) (number average molecular weight), M_(w)(weight average molecular weight) and molecular weight distributions d(M_(w)/M_(n)), and d′ (M_(z)/M_(w)) were determined by size exclusionchromatography (SEC) and in particular by gel permeation chromatography(GPC). Briefly, a GPC-IR5 from Polymer Char was used: 10 mg polymersample was dissolved at 160° C. in 10 ml of trichlorobenzene for 1 hour.Injection volume: about 400 μl, automatic sample preparation andinjection temperature: 160° C. Column temperature: 145° C. Detectortemperature: 160° C. Two Shodex AT-806MS (Showa Denko) and one StyragelHT6E (Waters) columns were used with a flow rate of 1 ml/min. Detector:Infrared detector (2800-3000 cm⁻¹). Calibration: narrow standards ofpolystyrene (PS) (commercially available). Calculation of molecularweight M_(i) of each fraction i of eluted polymer is based on theMark-Houwink relation (log₁₀(M_(PE))=0.965909×log 10(M_(PS))−0.28264)(cut off on the low molecular weight end at M_(PE)=1000).

The molecular weight averages used in establishing molecularweight/property relationships are the number average (M_(n)), weightaverage (M_(w)) and z average (M_(z)) molecular weight. These averagesare defined by the following expressions and are determined form thecalculated M_(i):

$M_{n} = {\frac{\sum\limits_{i}{N_{i}M_{i}}}{\sum\limits_{i}N_{i}} = {\frac{\sum\limits_{i}W_{i}}{\sum\limits_{i}{W_{i}/M_{i}}} = \frac{\sum\limits_{i}h_{i}}{\sum\limits_{i}{h_{i}/M_{i}}}}}$$M_{w} = {\frac{\sum\limits_{i}{N_{i}M_{i}^{2}}}{\sum\limits_{i}{N_{i}M_{i}}} = {\frac{\sum\limits_{i}{W_{i}M_{i}}}{\sum\limits_{i}W_{i}} = \frac{\sum\limits_{i}{h_{i}M_{i}}}{\sum\limits_{i}h_{i}}}}$$M_{z} = {\frac{\sum\limits_{i}{N_{i}M_{i}^{3}}}{\sum\limits_{i}{N_{i}M_{i}^{2}}} = {\frac{\sum\limits_{i}{W_{i}M_{i}^{2}}}{\sum\limits_{i}{W_{i}M_{i}}} = \frac{\sum\limits_{i}{h_{i}M_{i}^{2}}}{\sum\limits_{i}{h_{i}M_{i}}}}}$

Here N_(i) and W_(i) are the number and weight, respectively, ofmolecules having molecular weight M_(i). The third representation ineach case (farthest right) defines how one obtains these averages fromSEC chromatograms. hi is the height (from baseline) of the SEC curve atthe i_(th)elution fraction and M_(i) is the molecular weight of specieseluting at this increment.

Rheology long chain branching index g_(rheo) was measured according tothe formula, as described in WO 2008/113680:

${g_{rheo}({PE})} = \frac{M_{w}({SEC})}{M_{w}\left( {\eta_{o},{MWD},{SCB}} \right)}$

wherein Mw (SEC) is the weight average molecular weight obtained fromsize exclusion chromatography expressed in kDa; and wherein Mw (η₀, MWD,SCB) is determined according to the following, also expressed in kDa:

M _(w)(η₀ ,MWD,SCB)=exp(1.7789+0.199769LnM _(n)+0.209026(Lnη_(o))+0.955(ln ρ)−0.007561(LnM _(z))(Ln η_(o))+0.02355(ln M _(z))²)

wherein the zero shear viscosity η₀ in Pa·s is obtained from a frequencysweep experiment combined with a creep experiment, in order to extendthe frequency range to values down to 10⁻⁴ s⁻¹ or lower, and taking theusual assumption of equivalence of angular frequency (rad/s) and shearrate; wherein zero shear viscosity η₀ is estimated by fitting withCarreau-Yasuda flow curve (η−W) at a temperature of 190° C., obtained byoscillatory shear rheology on ARES-G2 equipment (manufactured by TAInstruments) in the linear viscoelasticity domain; wherein circularfrequency (W in rad/s) varies from 0.05-0.1 rad/s to 250-500 rad/s,typically 0.1 to 250 rad/s, and the shear strain is typically 10%. Inpractice, the creep experiment is carried out at a temperature of 190°C. under nitrogen atmosphere with a stress level such that after 1200 sthe total strain is less than 20%; wherein the apparatus used is anAR-G2 manufactured by TA instruments.

The total co-monomer content, especially 1-hexene (wt % C6) relative tothe total weight of the ethylene polymer and the molar fraction ofhexene co-monomer in sequences of length one relative to the co-monomercontent are determined by ¹³C NMR analysis according to the state of theart of ¹³C NMR analysis of ethylene based polyolefins.

The ¹³C NMR analysis was performed under conditions such that the signalintensity in the spectrum is directly proportional to the total numberof contributing carbon atoms in the sample. Such conditions are wellknown to the skilled person and include for example sufficientrelaxation time etc. In practice, the intensity of a signal is obtainedfrom its integral, i.e. the corresponding area. The data were acquiredusing proton decoupling, several hundred even thousands scans perspectrum, at a temperature of 130° C. The sample was prepared bydissolving a sufficient amount of polymer in 1,2,4-trichlorobenzene (TCB99% spectroscopic grade) at 130° C. and occasional agitation tohomogenize the sample, followed by the addition of hexadeuterobenzene(C₆D₆, spectroscopic grade) and a minor amount of hexamethyldisiloxane(HMDS, 99.5+%), with HMDS serving as internal standard. To give anexample, about 200 to 600 mg of polymer were dissolved in 2.0 ml of TCB,followed by addition of 0.5 ml of C6D6 and 2 to 3 drops of HMDS. Thechemical shifts are referenced to the signal of the internal standardHMDS, which is assigned a value of 2.03 ppm. ¹³C NMR observed signalsare assigned according to the co-monomer involved and correspondingliterature. The following non-exhaustive literature references can beused: G. J. Ray et al. in Macromolecules, vol 10, no 4, 1977, p. 773-778and Y. D Zhang et al in Polymer Journal, vol 35, no 7, 2003, p. 551-559.The total co-monomer content relative to the total weight of ethylenepolymer is determined from the appropriate peaks area combination, awell-known method to the skilled person.

Structure of Catalysts:

1. Metallocene 1

Dichloro[rac-ethylenebis(4,5,6-tetrahydro-1-indenyl)]zirconium waspurchased from Boulder Scientific Company (CAS 100163-29-9).

2. Metallocene 2 Bis(nBuCp)HfCl₂

Bis(n-butylcyclopentadienyl)hafnium dichloride was purchased fromChemtura (CAS 85722-08-3).

3. Metallocene 3

This metallocene was synthesized as described in U.S. Pat. No. 6,376,418B1.

4. Metallocene 4

Metallocene 4 was prepared as described below and as shown underScheme 1. Unless otherwise stated, all syntheses were performed undernitrogen atmosphere using dry solvents.

Step 1:

To a solution of 3.52 g (0.022 mol) of diethyl malonate in 25 ml of THF,0.88 g (60% in oil, 0.022 mol) of sodium hydride was added at 0° C. Thismixture was refluxed for 1 hour and then cooled to room temperature.Then, 5 g (0.022 mol) of 4-tBu-benzylbromide was added, and theresulting mixture was refluxed for 3 hours. A precipitate formed (NaBr).This mixture was cooled to ambient temperature and filtered through aglass frit (G2). The precipitate (NaBr) was additionally washed with 3×5ml of THF. The combined filtrates were evaporated to dryness andcompound was used without further purification.

The residue was dissolved in 20 ml of ethanol and 2.5 ml of water wereadded then 8 g of potassium hydroxide at 0° C. The resulting mixture wasrefluxed for 2 h, and then 10 ml of water was added. Ethanol wasdistilled off under reduced pressure and controlled temperature (max 30°C.). The resulting aqueous solution was acidified with HCl to pH 1 andthe product was extracted with ether (3×100 mL). The combined organicfractions were washed with HCl 1 M (1×25 ml) and brine (1×25 ml) thendried over MgSO₄ and concentrated under reduced pressure and compoundwas used without further purification.

The product was decarboxylated by heating for 2 hours at 160° C. (a gasevolution was noticed). The product obtained was dissolved in 30 ml ofdichloromethane, and 30 ml of SOCl₂ was added. The mixture was refluxedfor 3 hours and then evaporated to dryness.

The residue was dissolved in 12 ml of dry dichloromethane, and thesolution obtained was added dropwise to a suspension of 6.5 g (0.05 mol)of AlCl₃ in 68 ml of dichloromethane for 1 hour at 0° C., whilevigorously stirring. Then, the reaction mixture was refluxed for 3hours, cooled to ambient temperature, poured on 250 cm³ of ice, andextracted with DCM (3×50 ml).

The organic layer was washed with HCl 1M and brine (1×25 ml each). Thecombined organic fractions were dried over MgSO₄ and then evaporated todryness. The product was isolated by filtration over silica (1 to 10%AcOEt in isopentane). The desired product was a yellow oil (Yield=35%).

¹H NMR (500 MHz, CDCl₃) δ: 1.35 (s, 9H; CH₃); 2.72 (m, 2H, CH₂-Ph); 3.10(m, 2H, CH₂—C═O); 7.44 (m, 1H, CHar.); 7.67 (m, 1H, CHar.); 7.79 (m, 1H,CHar.)

Step 2:

6-tBu-1-indanone (1 eq., 5.078 g) was dissolved in 80 mL of Et₂O. PhMgBr(1.1 eq., 10 mL, 3M) was added at 0° C. dropwise and the solution washeated at reflux during 2 hours and then stirred overnight at roomtemperature. After overnight stirring, the reaction was slowly quenchedwith 50 mL of 1 M HCl and stirred during 1 hour. The mixture wasneutralized with saturated solution of NaHCO₃ and extracted with diethylether (×2). The combined organic layer was dried over magnesium sulfateand the solvent was removed under reduced pressure. The product wasisolated as a slightly yellow oil (6.54 g, 95%) and used withoutpurification.

Step 3:

2 g (8 mmol) of 6-tBu-(phenyl)-1-indene were introduced into 50 mL ofdiethyl ether, and 5.3 mL of n-butyllithium (1.6 M in hexane) was addeddropwise at 0° C. After this addition was complete, the mixture wasstirred at room temperature overnight. A catalytic amount of CuCN (5 mol%) was added and the resulting solution was stirred during 30 minutesthen 0.49 mL of (dimethyl)dichlorosilane (4 mmol) were added in oneportion. After this addition, the reaction solution was stirredovernight at room temperature. The reaction mixture was filtered throughalumina and the solvent was removed in vaccuo. The product was purifiedby silica gel flash column chromatography with hexane/DCM (9/1) aseluent to obtain an orange powder. Yield=52%.

¹H NMR (500 MHz, CDCl₃) δ: −0.15 (s, 6H, CH₃Si); 1.35 (s, 18H, (CH₃)₃C);3.69 (d, J=7 Hz, 2H, CH—Si); 6.32 (d, J=7 Hz, 2H, CH═); 7.30 (m, 2H,CHar.); 7.35-7.48 (m, 8H, CHar.); 7.61 (m, 4H, CHar.); 7.70 (m, 2 h,CHar.)

Step 4:

In a glove-box, 0.43 g of bis-indenyl proligand was introduced in aflask and 20 mL of diethyl ether was added. 0.54 mL of n-butyllithiumsolution (1.6 M in hexane) was added dropwise at room temperature. Afterthis addition was complete, the mixture was stirred overnight at thistemperature. Solvent was removed, the solid was washed with pentanetwice and then dry pentane (20 mL) was added. 0.181 g of zirconiumtetrachloride (1 eq.) was added in small portions. The solution wasstirred for two days at room temperature. The precipitate that forms wasseparated by filtration and washed twice with pentane. Solvent wasremoved and the resulting orange solid was dried under vacuum (0.365 g).The desired complex was obtained as a rac/meso ratio of 1/1 and was usedas such in the polymerization experiments. Yield=33%.

¹H NMR (500 MHz, CD₂C₂) δ 0.91 (s, 6H, CH₃Si); 1.32 (s, 18H, CH₃—C);6.05 (s, 2H, CHar.); 7.05-7.20 (m, 2H, CHar.); 7.20-7.30 (m, 2H, CHar.);7.40 (m, 4H, CHar.); 7.55 (m, 4H, CHar.); 7.68 (s, 2H, CHar.); 7.97 (m,2H, CHar.)

5. Metallocene 5 (Butenyl)MeC(Cp)(2,7-tBu2-Flu)ZrCl2

Metallocene 5 was prepared as described below, following the synthesisdescribed in Journal of Organometallic Chemistry vol. 553, 1998, p.205-220:

(5) Step 1:

Into a 200 mL 3-neck flask equipped with a gas inlet tube and a magneticstirring bar was charged, under nitrogen, 2.5 eq of freshly crackedcyclopentadiene and 1 eq of 5-hexene-2-one in 60 mL of methanol. Then, 2eq of pyrrolidine was added dropwise at 0° C. and the mixture wasstirred overnight at room temperature. The reaction was quenched with 50mL of HCl 1M and extracted with Et₂O (3×50 mL). Organic fractions weredried over MgSO₄ and solvent was removed under reduced pressure. Thefulvene was obtained as a yellow oil and used without furtherpurification (Yield=65%).

Step 2:

In a 3-neck flask, 1 eq of di-tert-butylfluorene was added under flow ofnitrogen and dissolved in 70 mL of Et₂O. 1.1 eq of n-BuLi (1.6M inhexane) was added dropwise at 0° C. to this solution and the mixture wasstirred overnight at room temperature. A solution of 3.5 g of fulveneprepared in the previous step, dissolved in 30 mL of Et₂O was addeddropwise. The reaction mixture was allowed to stir overnight. Reactionwas quenched with water and extracted with Et₂O (3×50 mL). Combinedorganic fractions were dried over MgSO₄ and solvent was removed underreduced pressure. The product was crystallized in pentane/MeOH at 0° C.to afford a white solid (Yield=85%).

Step 3:

In a round-bottomed flask, 1 g of ligand was introduced and dissolved in40 mL of Et₂O. 2.1 eq. of nBuLi was added dropwise and the mixture wasstirred overnight at room temperature. Solvent was removed under vacuumand 40 mL of dry pentane was added. Then 1 eq of ZrCl₄ was added insmall portions at room temperature. The reaction was stirred over 2 daysand filtered. The resulting precipitate was diluted in DCM andcentrifuged to eliminate lithium chloride. Solvent was removed undervacuum to afford a pink-red powder (Yield=70%).

¹H NMR (500 MHz, CD₂Cl₂) δ 1.34 (s, 9H, CH₃ tBu); 1.36 (s, 9H, CH₃ tBu);2.30 (m, CH₂ alk); 2.43 (s, 3H, CH₃); 2.55 (m, 1H, CH₂ alk.); 2.65 (m,1H, CH₂ alk.); 3.25 (m, 1H, CH₂ alk.); 5.13 (m; 1H, CHvinyl); 5.18 (m;1H, CHvinyl); 5.70 (m, 2H, CHcp); 6.10 (m; 1H, CHvinyl); 6.29 (m, 2H,CHcp); 7.55 (s, 1H, CHflu), 7.63-7.68 (m, 2H, CHflu); 7.72 (s, 1H,CHflu); 8.00-8.04 (m, 2H, CHflu)

6. Metallocene 6: EBI Catalyst

Dichloro[rac-ethylenebis(1-indenyl)]zirconium was purchased from MCATGmbh (CAS 100080-82-8).

7. Synthesis of Supported Catalysts

All catalyst and co-catalyst experimentations were carried out in aglove box under nitrogen atmosphere. Methylaluminoxane (30 wt %) (MAO)in toluene from Albemarle was used as the activator. Titanated silicafrom PQ (PD12052) was used as catalyst support (D50: 25 μm).

Supported metallocene catalysts were prepared in two steps using thefollowing method:

1. Impregnation of MAO on Silica:

Ten grams of dry silica (dried at 450° C. under nitrogen during 6 h) wasintroduced into a round-bottomed flask equipped with a mechanicalstirrer and a slurry was formed by adding 100 ml of toluene. MAO (21 ml)was added dropwise with a dropping funnel. The reaction mixture wasstirred at 110° C. during 4 hours. The reaction mixture was filteredthrough a glass frit and the powder was washed with dry toluene (3×20ml) and with dry pentane (3×20 ml). The powder was dried under reducedpressure overnight to obtain a free flowing grey powder.

2. Deposition of Metallocene on Silica/MAO Support:

Silica/MAO (10 g) was suspended in toluene (100 ml) under nitrogen.Metallocenes A and B (total amount of metallocene=0.2 g) were introducedand the mixture was stirred 2 hours at room temperature. The reactionmixture was filtered through a glass frit and the powder was washed withdry toluene (3×20 ml) and with dry pentane (3 times). The powder wasdried under reduced pressure overnight to obtain a free flowing greypowder.

The catalyst compositions prepared are shown in Table 1.

TABLE 1 Catalyst Composition Ratio catalyst A:catalyst B Met 4/Met 2 1:1Met 3/Met 1 1:1 Met 3/Met 2 1:4 Met 2/Met 5 4:1 Met 1/Met 5 1:1 Met4/Met 5 1.5:1  Met 6/Met 5 1:1

8. Polymerizations

Polymerization reactions were performed in a 132 ml autoclave with anagitator, a temperature controller and inlets for feeding of ethyleneand hydrogen. The reactor was dried at 110° C. with nitrogen during onehour and then cooled to 40° C.

All polymerizations were performed under the conditions depicted intable 2 (unless otherwise stated). The reactor was loaded with 75 ml ofisobutane, 1.6 ml of 1-hexene and pressurized with 23.8 bar of ethylenewith 800 ppm of hydrogen. Catalyst (3.5 mg) was added. Polymerizationstarted upon catalyst suspension injection, was performed at 85° C. andwas stopped after 60 minutes by reactor depressurization. Reactor wasflushed with nitrogen prior opening.

TABLE 2 Conditions Unit Reactor Isobutane (iC4) L     0.075Triisobutylaluminum (TIBAL) ppm 100 1-hexene wt %*    2.44 Hydrogen ppm 800** Temperature ° C.  85 Ethylene pressure bar   23.8 *In comparisonto iC4 **in ethylene feed

The results for the single catalysts are shown in Table 3.

TABLE 3 Polymerization of ethylene with single catalysts Activity Ml₂M_(n) M_(w) M_(z) Tm Density % wt Catalyst (g/g/h) (g/10 min) (kDa)(kDa) (kDa) M_(w)/M_(n) M_(z)/M_(w) (° C.) g/cm³ grheo C6 Met 1 6477 1.029.1 77.4 154.7 2.7 2.0 121.0 0.936 0.77 3.1 Met 2 462 2.1 28.1 87.4671.0 3.1 7.7 121.4 0.935 0.95 3.3 Met 3 3040 37.5 12.2 43.8 173.7 3.64.0 118.9 0.939 0.81 5.4 Met 4 2678 50.4 9.8 36.2 493.1 3.7 13.6 127.80.958 0.72 0.6 Met 5 4787 0.5 50.4 124.1 294.7 2.5 2.4 112.4 0.917 0.827.9 Met 6 7925 1.5 19.1 106.8 422.5 5.6 4.4 119.4 0.938 0.59 4.6

The results for the dual catalysts are shown in Tables 4 and 5.

TABLE 4 Polymerization of ethylene with dual catalysts Ratio ActivityMl₂ M_(n) M_(w) M_(z) Tm % wt Example Composition catalyst (g/g/h) (g/10min) (kDa) (kDa) (kDa) M_(w)/M_(n) M_(z)/M_(w) (° C.) Density grheo C61(comparative) Met4/Met2 1:1 740 17.5 11 43 674 3.9 15.6 126.6 0.954 —2.8 2(comparative) Met3/Met1 1:1 6307 1.2 27 75 143 2.8 2.0 123.9 0.9400.75 3.2 3(comparative) Met3/Met2 1:4 1362 3.0 15 65 208 4.4 3.2 122.00.942 0.80 2.8 4(comparative) Met2/Met5 4:1 2590 0.1 46 188 562 4.1 3.0119.1 0.933 0.76 2.8 5 Met1/Met5 1:1 7164 0.1 27 140 437 5.2 3.1 122.70.938 0.90 4.3 6 Met4/Met5 1.5:1  2320 0.1 26 157 560 6.1 3.6 119.90.934 0.79 5.4 7(comparative) Met6/Met5 1:1 10881 0.2 26 119 344 4.5 2.9122.1 0.935 0.88 3.9

TABLE 5 Polymerization of ethylene with dual catalysts Ratio H₂ ActivityMl₂ Mn Mw Mz Density Example Composition catalyst (ppm) (g/g/h) (g/10min) (kDa) (kDa) (kDa) M_(w)/M_(n) M_(z)/M_(w) Tm (° C.) g/cm³ grheo 8Met4/Met5 1.5:1 800 4800 0.6 16 127 510 7.9 4 126.1 0.947 0.76

The activity as a function of hydrogen concentration was also studiedfor three catalyst compositions with different ratio of Met1/Met5. Thepolymerization conditions were the same as listed in Table 2 except forthe hydrogen concentration. The results are shown in FIG. 1.

The activity as a function of hydrogen concentration was also studiedfor a catalyst composition Met4/Met5 1.5:1 (60/40) ratio. Thepolymerization conditions were the same as listed in Table 2. Theresults are shown in FIG. 3.

The melt flow as a function of hydrogen concentration was also studiedfor catalyst composition Met4/Met5 1.5:1 (60/40) ratio. Thepolymerization conditions were the same as listed in Table 2 except forthe hydrogen concentration. The results are shown in FIG. 4.

Several families of supported dual catalyst were synthesized andcompared with the corresponding single-site catalysts. Polymerizationsresults revealed a broadening of polymer molecular weight distributionfor the catalyst compositions according to the invention and an increaseof activity for most of them. Moreover, the “inverse comonomer”incorporation, which would improve polymer mechanical properties, wasobserved for two combinations: Met1/Met5 and Met4/Met5 (Examples 5, 6and 8) (see GPC-IR FIGS. 2, 5 and 7, polymerization conditions same aslisted in Tables 4 and 5), in contrast with comparative example 7 usingcombination Met6/Met5 (FIG. 6).

1.-15. (canceled)
 16. A catalyst composition comprising: catalystcomponent A comprising a bridged metallocene compound with two indenylgroups each indenyl being independently substituted with one or moresubstituents, wherein at least one of the substituent is an aryl orheteroaryl; catalyst component B comprising a bridged metallocenecompound with a substituted or unsubstituted cyclopentadienyl group anda substituted or unsubstituted fluorenyl group; an optional activator;an optional support; and an optional co-catalyst.
 17. The compositionaccording to claim 16, wherein the bridged metallocene compound ofcatalyst component B comprises at least one alkenyl, cycloalkenyl, orcycloalkenylalkyl substituent.
 18. The composition according to claim16, wherein the bridged metallocene compound of catalyst component Bcomprises at least one alkenyl, cycloalkenyl, or cycloalkenylalkylsubstituent on the bridge.
 19. The composition according to claim 16,wherein catalyst component B contains a C, Si, Ge, or B bridging atom.20. The composition according to claim 16, wherein the activatorcomprises an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, or any combination thereof. 21.The composition according to claim 16, wherein the catalyst compositioncomprises a co-catalyst.
 22. The composition according to claim 16,wherein the catalyst composition comprises an organoaluminum co-catalystselected from the group comprising trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and any combinationthereof.
 23. The composition according to claim 16, wherein the supportcomprises a solid oxide, wherein the solid oxide comprises titanatedsilica, silica, alumina, silica-alumina, silica-coated alumina, aluminumphosphate, aluminophosphate, heteropolytungstate, titania, zirconia,magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixturethereof.
 24. The composition according to claim 16, comprising analumoxane activator; and a titanated silica or silica solid support; andan optional co-catalyst.
 25. The composition according to claim 16,wherein catalyst component A comprises a bridged metallocene catalyst offormula (I), wherein

each of R¹, and R³, are independently selected from the group consistingof alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl,alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)₃, heteroalkyl; wherein atleast one of R¹ or R³ is aryl, wherein each R¹⁰ is independentlyhydrogen, alkyl, or alkenyl; and m, n, p, q are each independently aninteger selected from 0, 1, 2, 3, or 4; each of R², and R⁴, areindependently selected from the group consisting of alkyl, alkenyl,cycloalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkoxy, alkylaryl,arylalkyl, halogen, Si(R¹⁰)₃, heteroalkyl; wherein at least one of R² orR⁴ is aryl, wherein each R¹⁰ is independently hydrogen, alkyl, oralkenyl; and m, n, p, q are each independently an integer selected from0, 1, 2, 3, or 4; L¹ is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein his an integer selected from 1, 2, or 3; each of R⁸, and R⁹ areindependently selected from the group comprising hydrogen, alkyl,alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl,and arylalkyl; or R⁸ and R⁹ together with the atom to which they areattached form a cycloalkyl, cycloalkenyl or heterocyclyl; M¹ is atransition metal selected from the group consisting of zirconium,titanium, hafnium, and vanadium; and Q¹ and Q² are each independentlyselected from the group consisting of halogen, alkyl, —N(R¹¹)₂, alkoxy,cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, andheteroalkyl; wherein R¹¹ is hydrogen or alkyl.
 26. The compositionaccording to claim 16, wherein the catalyst component A contains aSiR⁸R⁹, or —[CR⁸R⁹]_(h)— bridging group; wherein h is an integerselected from 1, 2, or 3; each of R⁸, and R⁹ are independently selectedfrom the group comprising hydrogen, alkyl, alkenyl, cycloalkyl,cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R⁸and R⁹ together with the atom to which they are attached form acycloalkyl, cycloalkenyl or heterocyclyl.
 27. The composition accordingto claim 16, wherein catalyst component B comprises a bridgedmetallocene catalyst of formula (II), wherein

each of R⁵, R⁶, and R⁷, are independently selected from the groupconsisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl,cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen,Si(R¹⁰)₃, heteroalkyl; wherein each R¹⁰ is independently hydrogen,alkyl, or alkenyl; and r, s, t are each independently an integerselected from 0, 1, 2, 3, or 4; L² is —[CR⁸R⁹]_(h)—, SiR⁸R⁹, GeR⁸R⁹, orBR⁸; wherein h is an integer selected from 1, 2, or 3; each of R⁸, andR⁹ are independently selected from the group comprising hydrogen, alkyl,alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl,and arylalkyl; or R⁸ and R⁹ together with the atom to which they areattached form a cycloalkyl, cycloalkenyl or heterocyclyl; M² is atransition metal selected from the group consisting of zirconium,titanium, hafnium, and vanadium; and Q³ and Q⁴ are each independentlyselected from the group consisting of halogen, alkyl, —N(R¹¹)₂, alkoxy,cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, andheteroalkyl; wherein R¹¹ is hydrogen or alkyl.
 28. An olefinpolymerization process, the process comprising: contacting a catalystcomposition according to claim 16, with an olefin monomer, optionallyhydrogen, and optionally one or more olefin co-monomers; andpolymerizing the monomer, and the optionally one or more olefinco-monomers, in the presence of the at least one catalyst composition,and optional hydrogen, thereby obtaining a polyolefin.
 29. An olefinpolymer at least partially catalyzed by at least one catalystcomposition according to claim 16, or produced by the process accordingto claim
 28. 30. An article comprising the olefin polymer according toclaim 29.